Saturated linear copolymers



United States Patent 0 26,407 SATURATED LINEAR COPOLYMERS George B.Butler, Gainesville, Fla., assignor to Peninsular Chem Research, Inc.,Gainesville, Plan, a corporation of Florida No Drawing. Original No.3,320,216, dated May 16, 1967, Ser. No. 436,677, Mar. 2, 1965.Application for reissue July 28, 1967, Ser. No. 675,261

12 Claims. (Cl. 260-785) Matter enclosed in heavy brackets appears inthe original patent but forms no part of this reissue specification;matter printed in italics indicates the additions made by reissue.

This application is a continuation-in-part of my copending applicationSerial No. 59,816, filed October 3, 1960, which is in turn acontinuation-in-part of my application Serial No. 803,838, filed April3, 1959 ot prior applications now abandoned.

This invention is directed to novel saturated linear copolymeric highmolecular weight materials, and to processes for making the same. Moreparticularly, this invention is directed to saturated linear copolymershaving repeating units in the polymeric chain exemplified by thefollowing structure:

Xih it:

wherein A, X, X, X, X', R,, R R and n have the meaning, statedhereinafter.

The art of polymerization, copolymerization, and of polymeric andcopolymeric resins is highly developed in the use of both mono-olefinicand diolefinic monomeric reactants. Generally speaking, it is known thatan ethylenically unsaturated organic compound can be polymerized to formlongchain linear molecules, respective monomeric reactants adding toeach other across the respective carbon-carbon double bonds. It is alsogenerally known that diethylenically unsaturated organic compoundshaving two olefinic double bonds may be polymerized to form largemolecules having a crosslinked structure. It is also known that themono-olefinic and di-olefinic compounds may be copolymerized to formcross-linked large molecules, as a general matter. Crosslinkedstructures typically are formed because of the difunctionality of themonomer. In some cases this copolymerization reaction may be conductedso as to avoid cross-linking, but with the retention of one unreacteddouble bond in the di-olefinic comonomer so that the resulting copolymeris vulcanizable.

In my copending application, Serial No. 720,040, filed March 10, 1958, Ihave further described certain novel linear homopolymers formed by thefree radical polymerization of 1,6-di-unsaturated monomers. The linearhomopolymers to which that invention is directed generally havingrepeating units in the homopolymer molecule corresponding to thestructural formula,

B it t l wherein A represents a methylene or carbonyl radical; Brepresent a etc., radical; R represents an alkyl radical; R representsan alkyl, aryl halogen, or cyano radical.

Still other novel linear homopolyrners are described in copendingapplication, Serial No. 720,092, filed March 10, 1958, wherein thehomopolymers are composed of repeating units having the structuralformula,

wherein R, R and n have similar significance.

It will be observed that the homopolymers in each of those copendingapplications have generally linear structures, but that the chain iscomposed of a series of heterocyclic rings linked to each other througha methylene group, meta to the hetero-atom in the ring.

It is an object of the present invention to provide certain novelsaturated linear copolymers and a process for making the same.

More specifically, it is an object of this invention to provide novelsaturated linear copolymers wherein the repeating unit in the polymericchain has the structure,

wherein A, X, X, X", X', R R R and n have the meaning, discussedhereinafter.

It is a further object of this invention to provide novel saturatedlinear copolymers wherein the repeating unit in the polymeric chainhaving the above structure is further substituted by groups which may beconverted by hydrolysis or other means to carboxylic acid groups.

Still another object of this invention is to provide a process formaking the aforesaid copolymers.

Other objects of this invention will become apparent to those skilled inthe art from the following description thereof.

The novel saturated linear copolymers provided by the present inventionare formed by the copolymerization of 1,4-di-olefinically unsaturatedmonomers with mono-olefinically unsaturated monomers. The polymerizationreaction is believed to involve two separate propagation steps, thefirst is believed to involve a 2,5-free radical addition of amono-olefinic material across the di-olefinic reactant, and the secondstep a free radical reaction of the first product with a secondmono-olefinic molecule. It is observed that the instant copolymersgenerally contained approximately two moles of the mono-olefinicreactant for every mole of the di-oleiinic reactant. The mechanism forthe polymerization is believed to take place in the following manner(using divinyl ether and ethylene as examples):

termination linear copolymers In this mechanism Z. stands for a freeradical initiator. Step (1) may be called the initiation step, step (2)is a first intermolecular propagation step, step (3) is anintramolecular propagation step, and step (4) is a second intermolecularpropagation step. Step (5) is the repeated combination of steps (1),(2), (3) and (4), leading to the linear copolymer molecule, having itrepeating units, before termination of the chain reaction is reached.Termination occurs in the usual fashion for free radical chainpolymerization reactions, i.e. when the growing polymer chain reactswith a protonic free radical or other stopping radical.

This copolymerization reaction may be carried out under a wide varietyof conditions. The temperature used may vary from 0 to about 100 C., butis preferably elevated above room temperature and at a temperature offrom about 40 to about 75 C. is best. The reaction may also be conductedat either atmospheric pressure or under elevated pressures equivalent tothose autogenously developed under sealed bomb conditions. When thereaction is conducted at atmospheric pressure, it is convenient toproceed under reflux conditions, the boiling point of the reactionmedium providing the appropriate reaction temperature. On the otherhand, when conducting the reaction under autogenous pressure conditions,the temperature may be independently controlled as desired. Generallyspeaking, however, there is no critical limitation to the temperature orpressure for the reaction other than the decomposition temperature forthe monomer, and, as indicated for atmospheric pressure conditions, theboiling point of the reaction medium. Depending primarily on thetemperature, the reaction will generally be completed within a necessaryperiod of time of from about 1 to 24 hours, typically within about 2 to7 hours. Longer times may, of course, be used as for instance up toseveral days.

The polymerization reaction of this invention is carried out with themonomers in solution in a solvent, or in an aqueous emulsion. In thisprocedure it has also been found that the concentration of the monomersin solution must generally be at least about 15% by weight of the totalingredients in order for the reaction to proceed according to thisinvention. At lower concentrations, other interfering reactions occur,or the reaction fails to go to completion.

An example of such a case may be seen in Example 8V of US. Patent2,798,053 wherein maleic anhydride and divinyl ether were copolymerizedat a total monomer concentration of about 10%. The product from thatreaction does not show the characteristics of the compounds of thepresent invention, nor their structure. The product of that patentdissolved in water overnight with hydrolysis and infra-red studiesdemonstrate the presence of alcoholie hydroxyl groups after hydrolysis.The additional evidence of unsaturation before but no unsaturation afterhydrolysis, and the known ease of hydrolysis of vinyl ether linkagesindicates clearly that the product of the patent example had pendantvinyl ether linkages, substantially unreacted, so that the peculiarintra-molecular cyclization reaction of this invention did not occur.

These same components will, however, form the product of the presentinvention when reacted according to Example VIII herein.

The process of this invention may accordingly be conducted generally ina solvent or in an emulsion at total monomer concentration of from about15% to about 90%, preferably from about 20% to about 80%, depending onthe tendency of the monomer to homopolymerize. The most practicalconcentration range is from about 25% to about taking into account thefact that the copolymer product frequently precipitates to form aslurry, and stirring can become difficult in later stages of thereaction.

Generally any solvent, which is a solvent for the monomers, may be usedin the polymerization reaction. Examples of such solvents includearomatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene,etc. Other solvents which may be used include dioxane, ethers ofethylene glycols such as dimethyl ethylene glycol, diethyl ethyleneglycol, and alcohols such as methanol, ethanol, propanol, etc., andketones such as acetone, methylethylketone, diethylketone, and esterssuch as methylacetatc, cthylacetate, ethylpropionate, etc. It will, ofcourse, be understood that the solvent used is aliphatic-ally saturatedand substantially inert so far as participating in the polymerizationreaction is concerned. In addition, as will he brought out more fullyhereinafter, certain monomers which may be used in the instantcopolymerization processes contain reactive groups other than thecarbon-carbon double bonds. In such cases, it is important that thesolvent also be inert to such reactive groups on the monomericreactants. Generally speaking, the preferred solvents are the aromatichydrocarbons since they satisfy all the criteria.

The processes for producing the present copolymers will generally employcatalysts previously used in free radical olefinic polymerizations. Itis particularly advantageous to use peroxygen catalysts such asdi-tertiary butyl peroxide. Other peroxide catalysts include inorganicperoxides such as hydrogen peroxide and barium peroxide, etc.; andorganic peroxides such as various dialkyl peroxides, alkyl hydrogenperoxides and diacyl peroxides such as acetyl peroxide and benzoylperoxide as well as peracids, such as peracetic acid and perbenzoic acidand salts of inorganic per-acids such as ammonium and potassiumpersulfate. Cyclic peroxides can also be used such as tetralinhydroperoxide and cumene hydroperoxide. Other free radical catalystssuch as azo compounds, e.g. azoisobutyronitrile, and oxygen may beemployed as a polymerization catalyst.

In addition to using the peroxide catalysts mentioned above, a furtherembodiment of this invention involves the use of a Ziegler-typecatalyst. The general technique of carrying out the reaction will be thesame as where a peroxygen catalyst was used, but the Ziegler-typecatalyst will be most advantageous for the polymerization of thosemonomers which do not contain oxygen or similar electron donors.Gencrally, any Ziegler-type catalyst may be used. These are enumeratedin Belgian Patent 713,08i, to Ziegler, and include a mixture of a metalcompound, where the metal is a Group IVb, Vb, or Vlb metal with aberyllium or aluminum alkyl or aryl compound, or a beryllium or aluminumalkyl hydride or aryl hydride. Of the metal compounds forming the firstcomponent of the mixture titanium tetrachloride is preferred and thepreferred beryllium compound is dibutyl beryllium. Various alkyls,aluminums, and berylliums may be, of course, used with satisfactoryresults. In addition, magnesium and zinc alkyls may be used in place ofthe beryllium or alkyls. Among the Group IVb, Vb and Vlb metals whichcan be used, there may be mentioned zirconium, thorium, vanadium,chromium, molybdenum, tantalum, niobium, etc., in the form of theirchlorides, alkyls, hydrated oxides, bromides, acetates,acetylacctonates, oxalates, phosphates, oxybromides, etc.

When either a Ziegler-type catalyst or a peroxygen catalyst is employed,the catalyst will be used in a conventional catalytic amount.Conveniently, the amount of catalyst used may be within the range fromabout 0.5 to about but generally for purposes of effectiveness of thereaction and economy, no more than about 8% by weight of the monomer maybe used.

As hereinbefore stated, my invention utilizes as one of the monomericreactants a 1:4-diene. Such 1:4-diencs are particularly well exemplifiedby compounds such as divinyl ether, divinyl dimethyl silane, divinylcyclopentamethylene silane, divinyl sulfone, and 1:4-pentadiene. Theseare, however, only typical examples and a wide variety of l:4'dienes maybe employed in equivalent manner. The only structural requirement isthat the atom or atomic grouping intermediate the two carboncarbondouble bonds be such that the angles will permit formation of thesix-membered ring formed in the polymer. Thus, additional 1:4-dieneswhich may be used include Divinyldiphenylsilane,

Divinyldi-( cy anoethyl -silanc, Divinylcyclotetramethylenesilane,3,3-dimethyl-l,4-pentadiene, 2,4-dimethyl-l,4,-pentadiene,Divinylsulfide,

Divinylsulfoxide,

Diisopropenyl ether,

Di-n-propenyl ether,

Vinyl isopropenyl ether,

Vinyl propenyl ether,

Divinyl ketone,

Diisopropenyl ketone, Di-n-propenyl ketone,

Vinyl isopropenyl ketone,

Vinyl n-propenyl ketone, 3-carbomethoxy-l,4-pentadiene,3,3-dicarbomethoxy-1,4-pentadiene, 2,4-dichloro-1,4-pentadiene,2,4-dicyano-l,4-pentadiene, 2,4-diphenyl-l,4-pentadiene,2,4-dicarbomethoxy-1,4-pentadiene, 1,1-divinylcyclopentane,1,1-divinylcyclohexane, 2,4-difiuoro-1,4-pentadiene,

l ,4- perfiuoropentadienc, Divinylmethylamine, Divinylphenylamine,Divinylmethylamine oxide, Divinylphenylamine oxide,Divinyldimethylammonium chloride, Divinylmethylphenylammonium chloride,Divinylmethylphosphine, Divinylmethylphosphine oxide,Divinyldimethylphosphonium chloride, Divinylphenylphosphine,Divinylphenylphosphine oxide, Divinylmethylphenylphosphoniurn chloride,Divinylmethylarsine, Divinylphenylarsine,

Divinylmethylarsine oxide, Divinylphenylarsine oxide,Divinyldimethylarsonium chloride, Divinylmethylphenylarsonium chloride,Divinylmethylstibine, Divinylphenylstibine, Divinylmethylstibine oxide,Divinylphenylstibine oxide, Divinyldimethylstibonium chloride,Divinylmethylphenylstibonium chloride, Divinylsilane,Divinyldiethoxysilane, Divinyldichlorosilane, Divinylgermane,Divinyldicthoxygcrmane, Divinyldichlorogerrnane, Divinyldimcthylgermane, Divinyldiphenylgermane, Divinyldimcthyl tin, Divinyldiphenyltin, Divinyldiethoxy tin,

Divinyl tin dichloride, and Divinyldimcthyl lead.

Similarly, a wide variety of mono-olefinically unsaturated monomers maybe used in the practice of this invention. Typical examples of thesemonoleiines include vinyl acetate, acrylonitrile, maleic anhydride,fumaronitrile, furnaryl chloride, dimethyl fumarate, diethyl maleate,dimethyl fumarate, as well as the simplest mono olefines such asethylene, propylene, butene-l, butene-Z, etc. The only structuralrequirement for the monoolefin is that it be capable of participation incatalyzed polymerization reactions. Accordingly, any mono-olefin whichwill polymerize under a free radical initiation, may be used in thepractice of this invention. As further illustrative of suchmono-olefins, there may be mentioned styrene, methyl methacrylate,methyl acrylate, ethyl, acrylate, ethyl ethacrylate, vinyl chloride,vinylidene chloride, vinyl trimethyl silane, vinyl naphthalene, andvinyl methyl ether. Actually, and in general, suitable monoclefins whichmay be employed include those formed by replacing one of the vinyl (orsubstituted vinyl) groups in the above-described 1:4-dienes by the loweralkyl or aryl group.

Thus, the linear copolymers provided by this invention are those havinga repeating unit of the structure:

wherein A stands for an element of Groups IVa, Va and Vla of thePeriodic Table, the free valences (as in the case of S, C, Si, N, Sb,Sn, Ge, etc.) are attached to a radical which may be oxygen, hydrogen,lower alkyl, lower alkylene, al'rtoxy, cyano-lower alkyl, monocyclicaryl, carboxy-lower alkyl and halogen; wherein R and R may be any ofhydrogen, lower alkyloxy, carboxy lower alkyl, nitrile, orcarboxy-halide, or together R, and R may represent the anhydride radicalo o t 0 wherein R stands for hydrogen or lower alkyl; and wherein X, X,X", and X may be any of hydrogen, lower alkyl, monocyclic aryl, nitrile,halogen, and carboxy-lower alkyl.

The corresponding monomer materials may be copolymerized to form thepolymers of this invention by conducting the reaction in an aromatichydrocarbon solvent or a non-functional group containing solvents suchas dioxane or the diethyl ether or ethylene glycol, etc. When the1:4-diene and the mono-olefin being polymerized do not contain acondensation-reactive group, then the other solvents such as glycols,alcohols, ketones and esters mentioned hereinbefore, may also be used.However, when either the 1:4diene or the mono-olefin contains such acondensation-reactive group, then it is preferred to only use thearomatic hydrocarbon solvents. Otherwise, there is a possibility ofreaction between the growing polymer or the monomeric units thereof,with the solvent itself, leading to undesired materials and complexdifliculty separated products. By condensation-reactive group is meant agroup which will participate in a condensation reaction in the broadsense of the word, i.e. an ionic reaction between 2 molecules to form anew molecule, usually with the loss of a by-product. Such reactionsinclude esterification (loss of water), transesterification (loss ofalcohol), alcohol acid chloride esterification (loss of HCl), alcoholplus acid anhydride esterilication (here, formation of an adjacentcarboxyl group rather than actual loss of atomic components), nitrilealcoholysis, ketone alcoholysis, etc., as well as the aldol type ofcondensation. The proper selection of the solvent will be apparent toone skilled in the art from the foregoing description.

Preferably, the 1:4-diene used in the practice of my invention are thosewith a straight unsaturated chain of at most 6 atoms, and wherein thischain carries as substituent groups such as hydrogen, halogen, cyanolower alkyl, monocyclic aryl, carboxy, carboxy lower alkyl,carboxyhalide, and carbon-lower alkyl. The mono-olefin is preferably arelatively simple lower olefin, which may be regarded as ethylenesubstituted by groups such as hydrogen, lower alkyl, carboxyanhydride,carboxy lower alkyl, carbon-lower alkoxy, nitrile, halogen, loweralkoxy, and monoand di-cyclic aryl.

While the above description relates to the preferred embodiment of thisinvention, in some instances it may be desirable to form copolymerswherein the cyclic units are linked together through several of themono-olefinic units, by using a mono-olefin:di-olefinic reactant ratioof more than 2:1. Thus, the individual repeating units defined above maybe separated by units of the average formula.

XII/R3 .Lutl L 4 LJn-i X', R R R and n having the meanings stated above.

A further feature of my invention is that the copolymerization reactionis stereo specific, and consequently isotactic polymers are obtainedwhen unsymmetrical monoolefins are employed. For instance, two distinctisotactic linear acidic copolymers are obtained by copolymerization ofdivinyl ether with maleic anhydride, followed by hydrolysis of the acidanhydride group, and from copolymerization of divinyl ether with fumarylchloride, followed by hydrolysis of the acid chloride group, forming ineach case a carboxylic group-substituted linear copolymers.

Generally speaking, the polymers provided by my invention have amolecular weight above 5,000 and generally in the range of about 10,000to about 20,000 molecular weight units. The copolymers formed fromdivinyl silane and divinyl sulfone with maleic anhydride and analogousmono-olefins, usually have a molecular weight in the range of from about7,000 to about 10,000 molecular weight units. However, theabove-mentioned upper limits for the molecular weight are not absolutebut may be exceeded in a given set of polymerization conditions wherethe growing polymer chain remains in the solvent instead ofprecipitating therefrom. Generally, the polymers are fiberandfilm-forming materials, and the molecular weight is, accordingly, suchas to confer that functional property.

The linear copolymers provided by this invention are thus useful asfiberand film-forming materials, providing fibers which may be knittedor woven and used for the manufacture of cloth, and film which may beused as protective coatings or package wrappings, and not unlike theproperties of polypyrollidine (except of course for the absence of anamino group basic reactivity). In addition, those polymers provided bymy invention which have a side chain structure on the basic carbonskeleton of the repeating unit a radical which is, or can be, readilyconverted to a carboxylic acid group, or useful as soil conditioningagents. These latter polymers can be used to facilitate soil husbandry.The various copolymers are also useful as lubricants and lubricantadditives, pour point depressants, elastomers, molding resins, foamresins, adhesives, and as cross-linking agents (in themselves) for epoxyresins.

While the above discussion will make it clear that my invention is notlimited thereto, the following examples will illustrate preferredembodiments thereof and indicate the manner in which the linearcopolymers are formed according to my invention, it being understoodthat generally the conditions used for any given pair of a 1:4-diene ora mono-olefin, may be employed with any other selected pair of reactants(remembering, of course, known limita tions of certain catalyst systems,especially Ziegler-type catalysts which are not suitable for thepolymerization of monomers containing oxygen, sulfur, etc. atoms).

EXAMPLE I Linear copolymer of divinyl ether and vinyl acetate Distilledwater 100 ml. Aerosol OT 0.5 g. Potassium persulfate 0.1 g. Freshlydistilled vinyl acetate 17.2 g. (0.2 mole). Freshly distilled divinylether 7.0 g. (0.1 mole).

The components were charged to a pressure bottle and heated at 60-65 C.with constant agitation for two hours. The solution was cooled and thecopolymer precipitated by the addition of a saturated solution of:sodium chloride. After thorough washing, the product was dried, and wassoluble in most common organic solvents. It was slightly soft at roomtemperature.

Analysis.Calcd. for C H O C, 59.5%; H, 7.44%. Found: C, 59.49%; H,7.71%.

EXAMPLE II Linear copolymer of divinyldimethylsilane and acrylonitrileBenzene ml.

Freshly distilled acrylonitrile 6.7 g. (0.125 mole).Divinyldimethylsilane 7.0 g. (0.0625 mole). Benzoyl peroxide 1.0 g.

EXAMPLE III Linear copolymer of divinylcyclopentamethylenesilane andmaleic anhydride Benzene 75 ml. Maleic anhydride 12.25 mg. (0.125 mole).Divinylcyclopentamethylenesilane 9.5 g. (0.0625 mole). Benzoyl peroxide1.0 g.

The above components were charged to a suitable reaction vessel andrefluxed for four hours. The copolymer began to precipitate aften anhour as a white powder. After cooling, the product was isolated byfiltration, washed thoroughly with hot benzene and dried. M.P. 350 C. Itwas soluble in dimethylformamide, dimethyl sulfoxide, and dilute aqueoussodium hydroxide.

Analysis.Calcd. for C H O Si: C, 58.6%; H. 5.8%; Si, 8.1%. Found: C,57.9%; H, 6.25%; Si, 7.65%. The product is a spirocopolymer.

EXAMPLE IV Linear copolyrner of divinyl ether and acrylonitrileDistilled water 100 ml.

Aerosol OT 0.5 g. Potassium persulfate 0.1 g. Freshly distilledacrylonitrile 10.6 g. (0.2 mole).

Divinyl ether (freshly distilled) 7.0 g. (0.1 mole).

The ingredients were charged to a pressure bottle and heated at 60-65 C.with constant shaking for two hours. After cooling, the emulsion wasprecipitated by the addition of a saturated sodium chloride solution.The white precipitated copolymer was separated by filtration, and dried.It was found to he soluble in dimethylformamide.

Ana1ysis.-Calcd. for C H ON C, 68.2% H, 6.82%. Found; C, 65.1%; H,6.23%. The copolymer possesses a high melting point which ischaracteristic of most polymers containing ring structures in thebackbone of the polymer chain.

EXAMPLE V Linear copolymer of divinyl sulfone and maleic anhydrideBenzene 75 ml. Maleic anhydride 12.25 g. (0.125 mole). Divinyl sulfone7.4 g. (0.0625 mole). Benzoyl peroxide 1.0 g.

The above compounds were charged to a three-necked flask equipped with amechanical stirrer and reflux condenser, and refluxed for four hours.The solid copolymer began to precipitate after about an hour. Aftercooling, the product was separated by filtration, washed thoroughly withhot benzene and dried. It was found to be soluble in dimethylforrnamide,aqueous sodium hydroxide, and dimethyl sulfoxide, confirming its linearnature.

Analysis.-Calcd. for C H O S: S, 10.2%. Found: S, 7.55%. It melts above250 C.

EXAMPLE VI Linear copolymer of divinyldimethylsilane and maleicanhydride Benzene 75 ml.

Maleic anhydride 12.25 g. (0.125 mole). Divinyldimethylsilane 7.0 g.(0.0625 mole). Benzoyl peroxide 1.0 g.

EXAMPLE VII Linear copolymer of divinyl ether and fumaronitrile Xylene75 ml. Fumaronitrile 9.75 g. (0.125 mole).

Divinyl ether (freshly distilled) 8.75 g. (0.0625 mole). Benzoylperoxide 0.5 g.

Linear copolyrner of divinyl ether and maleic anhydride Xylene 150 ml.Maleic anhydride 24.5 g. (0.25 mole). Divinyl ether (freshly distilled)8.75 g. (0.125 mole).

Benzoyl peroxide 0.5 g.

The above components were charged to a suitable reaction vessel andheated at 65 C. for four hours. The copolymerization is quiteexothermic. After cooling, the insoluble, white powder was removed byfiltration, washed thoroughly with hot xylene and dried at 80 C. Theyield was 33 g. It was soluble in acetone and 10% NaOH solution. It wasfound to have an intrinsic viscosity of 0.175 in both dimethylformamideand two normal sodium hydroxide. It was analyzed for carbon and hydrogenand the following results obtained:

Analysis.-Calcd. for c u o C, 54.13%; H, 3.76%. Found: C, 53.99%; H,4.00%. Infrared analysis confirms the proposed structure for thiscopolymer.

EXAMPLE 1X Linear copolymer of divinyl ether and lumaryl chlorideBenzene 75 ml. Divinyl ether (freshly distilled) 7.0 g. (0.1 mole).Furnaryl chloride 30.6 g. (0.2 mole).

Benzoyl peroxide 1.0 g.

' derivatives of this linear copolymer. it can be cross linked byreaction with a dihydric alcohol or a primary or secondary diamine.

EXAMPLE X Linear copolymer of divinyl sulfone and dimethyl fumarateBenzene 100ml.

Dimethyl fumarate 28.8 g. (0.2 mole). Divinyl sulfone 11.8 g. (0.1mole). Benzoyl peroxide 1.0g.

The above components were charged to a pressure bottle and placed in ashaker, and heated at -65" C. for four hours with shaking. Aftercooling, the resulting solution was treated with an excess of hcptane toprecipitate the copolymer. The copolynier was insoluble in benzene, aswould be expected from the presence of the polar sulfone group, but itssolubility in diinethylformamide and dichlorobenzene confirms its linearnature.

EXAMPLE XI Linear copolymer of divinyl ether and diethyl rnalcateDistilled water 100ml. Aerosol OT 0.5 g. Potassium persulfate 0.1 g.Divinyl ether 7.0 g. (0.1 mole). Diethyl maleate 34.4 g. (0.1 mole).

The above compounds were charged to a pressure bottle, and heated at -70C. for two hours; with shaking.

EXAMPLE XII Linear copolymer of divinyldimethylsilane and fumarylchloride Benzene 75 ml. Fumaryl chloride 30.6 g. (0.2 mole).Divinyldimethylsilane 11.2 g. (0.1 mole). Benzoyl peroxide 1.0 g.

The above components were charged to a suitable reaction vessel whichwas protected from moisture, and which had previously been flushed withdry nitrogen. The solu tion was refluxed for six hours. The resultingsolution was evaporated to dryness to yield a dark brown copolymer. Itwas soluble in acetone, benzene, and dimethylsulfoxide.

EXAMPLE XIII Linear copolymer of divinylsulfone and dimethyl fumarateWater (distilled) 100 ml.

Aerosol OT 0.5 g.

Potassium persulfate 0.1 g. Divinylsulfone 11.8 g. (0.1 mole). Dimethylfumarate 28.8 g. (0.2 mole).

The above were charged to a pressure bottle and heated at 65-70 C. forthree hours with constant agitation. The resulting solution wasevaporated to yield the solid copolymer. It was insoluble in most commonorganic solvents, but was soluble in dichlorobenzene. It had a meltingpoint of 290 C., confirming its linear nature.

EXAMPLE XIV Linear copolymer of divinyldimethylsilanc and vinyl acetateBenzene 75 ml. Vinyl acetate (freshly distilled) 17.2 g. (0.2 mole).Divinyldimethylsilane 11.6 g. (0.1 mole). Benzoyl peroxide 1.0 g.

The above compounds were charged to a suitable reaction vessel andrefluxed for 6V2 hours. The resulting solution was evaporated undervacuum. After purification, the polymer was a low melting yellow solid,soluble in most common organic solvents, confirming its linear nature.

EXAMPLE XV Linear copolymer of divinyldimethylsilane and acrylonitrileDistilled water 100 ml. Aerosol OT 0.5 g. Potassium persulfate 0.1 g.

Acrylonitrile Divinyldimethylsilane 10.6 g. (0.2 mole). 11.2 g. (0.1mole).

The components were charged to a pressure bottle and heated for twohours at 65-70 C. with constant agitation. The emulsion was diluted at300 ml. and then saturated sodium chloride solution was added until thepolymer settled out. The white, solid product was filtered, washed withwarm water and dried overnight at 65 C. It was found to be soluble inodichlorobenzene.

12 EXAMPLE XVI Isooctane ml. Aluminum triethyl 0.52 g. Titaniumtetrachloride 0.29 g. 1,4-pentadiene 17 g. (0.25 mole). Ethylene 14 g.(0.5 mole).

The isooctane was chromatographed through an activated alumina column toremove olefinic material and distilled from sodium. In a dry box under adry nitrogen atmosphere, the aluminum triethyl-titanium tetrachloridecatalyst (molar ratio 3:1) was prepared. This solution was charged to asuitable pressure reaction vessel and the 1,4-pentadiene added. Alloperations were performed under a dry nitrogen atmosphere. After sealingthe vessel, anhydrous ethylene was admitted to the total pressurerequired for a total charge of 14 g. of ethylene; the reaction mixturewas then heated to 50 C. with agitation for a total time of seventy-twohours. After cooling, the solution was removed and the copolymer wasprecipitated by pouring the hydrocarbon solution into methanol. Thesolubility of the copolymer in the hydrocarbon solvent confirms itslinear non-cross-linked structure.

EXAMPLE XVII Hydrolysis of divinyl ether maleic anhydride copolymer A 5g. sample of the copolymer of Example VIII (divinyl ether and maleicanhydride) was added to 10 ml. of water and heated on a steam bath.After several minutes, the copolymer dissolved through hydrolysis of theanhydride rings to the polycarhoxylic acid. The polycarhoxylic acid wasfound to be soluble in water and to possess all of the expectedproperties of such a structure. Evaporation of the excess water undervacuum left the polycarboxylic acid as a clear, plastic, glass-likematerial which could be ground to a white powder. The hydrolysis wasalso accomplished by treating the copolymer with aqueous sodiumhydroxide, and neutralizing the sodium salt of the polycarboxylic acidwith mineral acid. The polycarhoxylic acid was found to have a neutralequivalent of 75.5.

If the copolymer of Example IX is similarly hydrolyzed to convert theacid chloride groups to carboxylic acid groups, a differentpolycarboxylic acid is obtained.

EXAMPLE XVIII Linear copolymer of 1,4-pentadiene and maleic anhydrideXylene 150 ml. 1,4-pentadiene 8.5 g. (0.125 mole). Maleic anhydride 24.5g. (0.25 mole). Benzoyl peroxide 0.5 g.

The solvent, monomers, and catalyst were charged to a suitable pressurereaction vessel and heated to 70 C. for fifteen hours with agitation.During the first hour of heating at the above temperature, the white,insoluble copolymer began to precipitate. After cooling, thexyleneinsoluble copolymer was removed by filtration, washed thoroughlywith hot xylene, and dried. It was found to be soluble in acetone,confirming its linear nature. The yield was quantitative.

EXAMPLE XIX Xylene 150 ml. Perfiuoro-l,4-pentadiene 26.5 g. (0.125mole). Tritluorochloroethylene 29.2 g. (0.25 mole). Trichloroacetylperoxide 0.5 g.

The above components were charged to a suitable pressure reaction vesseland heated to 70 C. for 48 hours, with agitation. During this time, thecyclic copolymer formed. After isolation, it was found to be fusible,and soluble in a number of solvents, confirming its linearnoncross-linked structure. Trilluorobromoethylene, andtetrafluoroethylene can be substituted for trifluorochloro- EXAMPLE XXXylene 150 ml. Perfluoro-l,4-pentadiene 26.5 g. (0.125 mole). Maleicanhydride 24.5 g. (0.25 mole).

Benzoyl peroxide 0.5 g.

The solvent monomers and catalyst were charged to a suitable reactionvessel and heated to 70 C. for 24 hours, with agitation. After cooling,the xylene-insolubly copolymer which formed was removed by filtration,washed with hot xylene, and dried. The yield was quantitative. Theproduct was soluble in a number of solvents, confirming its linearnature. The copolymer was found to be soluble in aqueous sodiumhydroxide, producing sodium salt of the copolymer by hydrolysis of theanhydride linkages.

In the process of this example or in that of Example XIX, theperfiuoro-1,4-pentadiene may be replaced by 2,4-dichloro-1,4-pentadieneor 1,1-dichloro-1,4-pentadienc to yield other halogenated copolymersaccording to the general formula previously indicated.

EXAMPLE XXI Linear copolymer of 3,3-dimethyl-1,4-pentadiene and maleicanhydride Xylene 150 ml. 3,3-dimethyl-1,4-pentadiene 12.0 g. (0.125mole). Maleic anhydride 24.5 g. (0.25 mole). Benzoyl peroxide 0.5 g.

The 3,3-dimethyl-1,4-pentadiene was prepared by the Method of Cialo andBurwell (J. Org. Chem. 23, 1063 (1958)). The solvent monomers andcatalyst were charged to a suitable pressure reaction vessel and heatedto 70 C. for fifteen hours with agitation. During the first hour ofheating, a white insoluble copolymer began to precipitate. After coolingthe xylene-insoluble copolymer was removed by filtration, washedthoroughly with hot xylene, and dried. It was found to be soluble inacetone, confirming its linear nature.

It will be appreciated that, while my invention has been particularlydescribed with reference to certain specific embodiments thereofequivalent procedures and materials may be used, and the principle andscope thereof is limited only by the following claims.

I claim:

1. Novel linear high molecular weight copolymers useful in formingmolded or fiber or film articles consisting essentially of the repeatingunit of the structure:

wherein A is an element selected from the group consisting of GroupsIVa, Va, and VIa of the Periodic Table, said groups including elements6, 7, and 8, respectively, the free valences of which, when A stands foran element other than oxygen, are satisfied by bonding to a radicalselected from the group consisting of oxygen, hydrogen, lower alkyl,lower alkylene, cyano-lower alkyl, monocyclic aryl, carboxylower alkyland halogen; wherein R and R are selected from the group consisting ofhydrogen, lower alkyloxy, carboxy lower alkyl, nitrile andcarboxyhalide, and together R and R represent [when A stands for anelement other than oxygen] the anhydride radical O O O O tiimiwherein Rstands for a member selected from the group consisting of hydrogen andlower alkyl; and wherein X, X, X", and X' are selected from the groupconsisting of hydrogen, lower alkyl, monocyclic aryl, nitrile, halogen,and carboxy-lower alkyl.

2. A linear copolymer according to claim 1 and having the repeating unitof the structure:

3 4. A linear copolymer according to claim 1 and having the repeatingunit of the structure:

l on,

oil

5 =0 5. A linear copolymer according to claim 1 and having the repeatingunit of the structure:

the repeating unit of the structure:

i on (7:0 c=o (HBO-2' 0 15 7. A process for the preparation of linearcopolymers consisting essentially of the repeating unit of thestructure:

wherein A is an element selected from the group consisting of GroupsIVa, Va, and VIa of the Periodic Table, the free valencies of which,when A stands for an element other than oxygen, are attached to aradical selected from the group consisting of oxygen, hydrogen, loweralkyl, lower alkylene, cyano-lower alkyl, monocyelic aryl,carboxy-lo'wer alkyl and halogen; wherein R and R are selected from thegroup consisting of hydrogen, lower alkyloxy, carboxy lower alkyl,nitrile and carboxyhalide, and together R and R represent, [when Astands for an element other than oxygen,] the anhydride radical g; 9C-Od wherein R stands for a member selected from the group consisting ofhydrogen and lower alkyl; and wherein X, X, X", and X'" are selectedfrom the group consisting of hydrogen, lower alkyl, monocyclic aryl,nitrile, halogen, and carboxy-lower alkyl, which comprisescopolymerizing approximately 1 molar part of a 1:4-die'ne monomer of theformula X! XII XI! III! XC'I=(JJ-A-JI=CX with approximately 2 molarparts of a monoolefin monomer having the formula Rl R;

16 where X, X, X, X', R R and R have the definitions stated above in thepresence of a catalytic amount of a free radical catalyst in a reactionmedium, at a total monomer concentration of at least about 15%, byweight, of the total ingredients, and at a temperature above 0 C. andbelow the decomposition of said monomers for a necessary period of timeof at least one hour.

8. The process of claim 7, wherein said temperature is from about 40 C.to about C.

9. The process of claim 7 further defined as conducted in an inertsolvent for said monomers.

10. The process of claim 7, wherein said copolymerization is carried outwith said monomers dispersed in aqueous emulsion.

11. The process of claim 7, wherein said catalyst is selected from thegroup consisting of benzoyl peroxide and a mixture of aluminum triethyltitanium tetrachloride.

12. The process of claim 7 wherein said catalyst is composed of amixture of aluminum triethyl titanium tetrachloride.

References Cited UNITED STATES PATENTS The following references, citedby the Examiner, are of record in the patented file of this patent orthe original patent.

2,532,583 12/1950 Tyran 260-86.1 2,619,491 11/1952 Smith 260-86.l2,798,053 7/1957 Brown 260-803 JOHEPH L. SCHOFER, Examiner.

C. A. HENDERSON, Assistant Examiner.

